CN104583762B - Platform unit for combining sensing pressure, temperature and humidity - Google Patents

Abstract

The invention provides modular platform unit, it includes the multiple sensors for combining sensing pressure, temperature and humidity.Especially, the sensor is made up of nano particle (MCNP) layer for the metallic cover cast in flexible substrates or rigid basement.Disclose for the integrated of artificial or electronic skin application platform unit.

Description

Platform unit for combining sensing pressure, temperature and humidity

Technical field

The present invention relates to a kind of platform unit, the platform unit includes multiple for detecting pressure, temperature and humidity Sensor comprising the metal nanoparticle that (cap) is coated with organic coating.

Background technology

Production biomimetic prosthetic or electronic skin are required to high-resolution and low-response time sensing pressure, humidity and temperature The large-scale sensor array of degree.These sensor arrays for being designed to the physics and chemical information for providing environment can be more Plant application to be utilized, the application such as medical prosthesis and robot industry.For example, artificial limb can be coated with artificial or electronics skin Skin, so that the tactile of different pressures horizontal versions is provided for user, and robot limb can be with the people of different sensitivity Work or electronic skin surface are integrated, to be allowed for processing the autonomous control of object.Robotic surgery, health monitoring and it is many its His potential application can benefit from having the artificial or electronic skin of different sensitivity to pressure, temperature and/or damp condition Use (Eltaib et al., Mechatronics2003,13,1163-1177；Lee et al., Mechatronics1999,9,1- 31；With Dargahi et al., Int.J.Med.Rob.Comp.Ass.Surg.2004,1,23-35).

The flexible sensor for being initially designed to the soft and flexible part of handheld consumer electronic product and display shows It is developed as ultra-thin health monitoring band (Tiwana et al., the Sens.Actuat.A that may be mounted on skin 2012,179,17-31；With Rogers et al., PNAS, 2009,106,10875-10876).Successfully illustrate flexible biography The low-power touch-sensing platforms of sensor, the platform is based on nano wire, CNT, nano particle, elastomeric dielectric layer and organic field effect Answer transistor (Takei et al., Nature Mater.2010,9,821-826；Herrmann et al., Appl.Phys.Lett.2007,91,183105；Siffalovic et al., Nanotech.2010,21,385702； Vossmeyer et al., Adv.Funct.Mater.2008,18,1611-1616；Maheshwari et al., Science, 2006, 312,1501-1504；Mannsfeld et al., Nature Mater.2010,9,859-864；Pang et al., Nature Mater.2012,11,795-801；Matsuzaki et al., Sens.Actuat.A 2008,148,1-9；Lacour et al., Annual International Conference of the IEEE on Engineering in Medicine and Biology Society(EMBC),2011,8373-8376；Someya et al., PNAS2004,101,9966-9970； Cosseddu et al., IEEE Elec.Dev.Lett.2012,33,113-115；Joseph et al., J.Phys.Chem.C2008, 112,12507-12514；Boland,J.Nat.Mater.2010,9,790-792；With Yu-Jen et al., IEEE Elec.Dev.Lett.2011,58,910-917)。

US 2011/0019373 disclose preferably apply in the terminal for sensing bar around in electric equipment Part and/or the arrangement for sensing the biometric variable of user.

US 2012/0062245 discloses a kind of equipment, and it includes：Dielectric structure, the dielectric structure include each other by Multiple elastomeric regions that spacer region separates, the elastomeric regions are configured and arranged in response to pressure, so as to compress simultaneously Therefore the effective dielectric constant of change corresponding with the compressive state of the elastomeric regions is shown；And sensing circuit, it is described Sensing circuit includes multiple sensors based on impedance, and each sensor for being based on impedance includes a part of dielectric structure and quilt It is configured and arranged to by the instruction for providing the pressure to putting on the dielectric structure adjacent to each sensor come in response to dielectric The change of constant.

In order to realize that flexible sensor is widely implemented as artificial or electronic skin, it is necessary to meet several requirements.First, These sensors need to provide dynamic range wide, and the dynamic range is possible to measure the low pressure for being used for wisp operation (i.e., 1-10KPa) and can measure high pressure (that is, 10-100KPa) for operating weight body.Secondly, these sensor requirements are same When measurement pressure (touch), humidity, temperature and/or compound presence Arregui et al., IEEE Sensors J.2002, ( 2,482-487；Cook et al., JPMC 2009,5,277-298；Shunfeng et al., IEEE Sensors J.2012,10, 856-862；Lopez-Higuera et al., J.Lightwave Tech.2011,29,587-608；Konvalina et al., ACS Appl.Mater.Interf.2012,4,317-325；Bay et al., J.S.Rob.Autom.Mag.IEEE1995,2,36-43； With Wang et al., Langmuir2010,26,618-632).It is additional that to require to include low-voltage/low-power operation (typically low In 5V), with (Tsung-Ching et al., J.Disp.Tech.2009,5,206- compatible with the conventional battery of portable set 215).Finally, these sensor requirements be easier, faster with more cost effective manufacturing technology, with provide they extensively should With.

Nano particle (MCNP) layer of metallic cover in flexible substrates is the high sensitivity of new generation for meeting these requirements Potential candidate (Herrmann et al., the Appl.Phys.Lett.2007,91,183105 of flexible sensor；Wang et al., Langmuir2010,26,618-632；Wuelfing et al., J.Phys.Chem.B2002,106,3139-3145；Haick, J.Phys.D2007,40,7173-7186；Tisch et al., MRS Bull.2010,35,797-803；Tisch et al., Rev.Chem.Eng.2010,26,171-179；Vossmeyer et al., Adv.Funct.Mater.2008,18,1611-1616； Farcau et al., J.Phys.Chem.C.2011,115,14494-14499；With Farcau et al., ACS Nano2011,5, 7137-7143).MCNP films electrical property index ground depend on grain spacing from.Therefore, MCNP depositions on a flexible substrate Allow to adjust resistance by stretching or by bending substrate.The geometry and engineering properties of substrate are divided between also influenceing particle From.For example, metal-enhanced fluorescence, optical property and low-angle X-ray spectroscopy (SAXS) study verified nanometer Grain is separated and depends on substrate-strain.Additionally, theoretical calculation has shown that sensitivity of the single sensor to haptic load can lead to The thickness of control substrate is crossed to adjust.

The WO 2009/066293 of some inventors of the invention, WO 2009/118739, WO2010/079490, WO 2011/148371st, WO 2012/023138, US 2012/0245434, US 2012/0245854 and US 2013/0034910 are public The device based on the nanoparticle conductive core coated with organic coating is opened, the device is used to detect volatility and fixedness Compound, particularly for diagnosing various diseases and illness.

Combination sensing pressure, temperature and humidity for multifunction electronic or artificial skin application exist do not meet always Demand.

The content of the invention

The invention provides a kind of platform unit that pressure, temperature and humidity are detected using sensor technology, the biography Sensor technology is based on the metal nanoparticle coated with organic coating.

The present invention is based in part on following having now surprisingly been found that：The sensor of the nano particle (MCNP) of metallic cover Pressure sensor is can serve as when depositing on a flexible substrate.When base of the use with different geometry and engineering properties During bottom, these sensors allow to detect the load of wide scope.Astoundingly, these sensors also provide super-sensitive temperature And moisture measurement such that it is able to physical and chemical factor parameter is detected in combination.These results provide new means to customize The sensing property of the modular matrix of MCNP sensors, to provide them as the purposes of artificial or electronic skin.

According to one side, the invention provides a kind of for detecting selected from by pressure, temperature, humidity and combinations thereof The platform unit of parameter, the platform unit includes：Multiple sensors, the sensor includes the metal coated with organic coating Nano particle, wherein the multiple sensor includes：At least one pressure sensor in the substrate of substantial flexibility is deposited on, Wherein described pressure sensor is configured to sensing and applies pressure thereon and in response to the pressing creation electric signal, and At least one temperature or humidity sensor, the temperature or humidity sensor are configured in response to temperature change or humidity change Form (conformation) change of the metal nanoparticle of the organic coating cladding is shown, and in response to described Metamorphosis generates electric signal, thus provides the detection to pressure, temperature, humidity or their combinations.In one embodiment, Detected while the platform unit is provided to pressure, temperature and humidity.

In some embodiments, the platform unit includes that at least three include the metal nano coated with organic coating The sensor of particle, wherein three sensors include the pressure sensor, the temperature that are deposited in the substrate of substantial flexibility Sensor and humidity sensor, wherein the pressure sensor is configured to sensing applies pressure thereon and in response to institute State pressing creation electric signal；The temperature sensor is configured in response to temperature change and shows that the organic coating is coated Metal nanoparticle metamorphosis and in response to the metamorphosis generate electric signal；The humidity sensor is configured Into the metamorphosis of the metal nanoparticle that the organic coating cladding is shown in response to humidity change, and in response to institute State metamorphosis generation electric signal.

In some embodiments, temperature and moisture sensors are configured in response in temperature change or humidity change Each independent form for showing the metal nanoparticle coated with organic coating changes.

In some embodiments, the substrate of substantial flexibility includes polymer.In a specific embodiment, the polymerization Thing is selected from polyimides, polyamide, polyimides, polyethylene, polyester, dimethyl silicone polymer, polyvinyl chloride and polystyrene.Often Plant possibility and represent single implementation method of the invention.In other embodiments, the substrate of substantial flexibility includes silicon rubber Glue.In still other implementation methods, the substrate of substantial flexibility includes silica.It would be recognized by those skilled in the art that By changing the material of the substrate for forming substantial flexibility, the pressure sensor of different load sensitivity can be obtained.

In other embodiments, the substrate of substantial flexibility is characterised by width range for about 0.01-10cm and thickness Degree scope is for about 20-500 μm.It would be recognized by those skilled in the art that the geometric parameter of the substrate of substantial flexibility can be used to The load sensitivity of control pressure sensor.

In each implementation method, pressure sensor be configured to generation and the substrate of substantial flexibility skew (deformation, Deflection proportional electric signal) is measured.In other embodiments, pressure sensor is configured to strain gauge, and it is by machine Tool skew is converted into electric signal.

In further embodiment, temperature or humidity sensor are deposited on substantial flexibility or substantially rigid base On bottom.Every kind of possibility represents single implementation method of the invention.In some embodiments, deposition has temperature or wet thereon The substrate for spending the substantial flexibility of sensor includes polymer, and the polymer is selected from polyimides, polyamide, polyimides, poly- Ethene, polyester, dimethyl silicone polymer, polyvinyl chloride and polystyrene.Every kind of possibility represents single implementation of the invention Mode.In still other implementation methods, deposition has the substantial flexibility or rigid substrate of temperature or humidity sensor thereon Comprising silica.In other embodiments, the substrate of substantial flexibility includes silicon rubber.In some embodiments, base Rigid substrate is selected from metal, insulator, semiconductor, semimetal and combinations thereof in sheet.Every kind of possibility represents list of the invention Only implementation method.In one embodiment, substantially rigid substrate includes the silica on silicon chip.In another reality Apply in mode, substantially rigid substrate includes substantially rigid polymer.In still another implementation method, substantially just Property substrate include tin indium oxide.

In additional implementation method, platform unit includes multiple electrodes comprising conductive material, the multiple electrode with Each sensor is coupled, for measuring the signal generated by the sensor.In each implementation method, between adjacent electrode Distance range is for about between 0.01mm and about 5mm.It would be recognized by those skilled in the art that limit sensing area adjacent electrode it Between distance can be used to the sensitivity for controlling sensor to the change of load, temperature and/or humidity.

In some embodiments, each sensor in platform unit with selected from capacitance sensor, resistance sensor, The form configuration of resistive chemisensor, impedance transducer and field effect transistor sensing device.Every kind of possibility represents Ben Fa Bright single implementation method.In the exemplary embodiment, each sensor in platform unit is configured as chemical resistance Device (chemiresistor).

In each implementation method, platform unit also include detection means, the detection means include for measure resistance, The dress of the change of conductance, alternating current (AC), frequency, electric capacity, impedance, inductance, mobility, potential, optical property or voltage threshold Put.Every kind of possibility represents single implementation method of the invention.

In still other implementation methods, metal nanoparticle is selected from Au, Ag, Ni, Co, Pt, Pd, Cu, Al and combinations thereof. Every kind of possibility represents single implementation method of the invention.In additional implementation method, metal nanoparticle is selected from Au/ The metal alloy of Ag, Au/Cu, Au/Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt/Rh, Ni/Co and Pt/Ni/Fe.Often Plant possibility and represent single implementation method of the invention.In the exemplary embodiment, metal nanoparticle is that golden (Au) receives Rice grain.

In other embodiments, the geometry of metal nanoparticle is selected from cube, spheroid and spheroid geometric form Shape.Every kind of possibility represents single implementation method of the invention.

In further embodiment, organic coating is comprising selected from alkyl hydrosulfide, aryl mercaptan, alkylaryl thiol, alkane Base mercaptides, omega-functionalized alkanethiol salt, arene thiolate, (γ-mercaptopropyi) trimethoxy silane, dialkyl group two The compound of sulfide and combinations thereof and its derivative.Every kind of possibility represents single implementation method of the invention.In example In property implementation method, organic coating is 2- nitro -4- TRIFLUORO-METHYL benzenethiols.It is organic in another illustrative embodiments Coating is 3- ethoxylated thiophenols.In still another example implementation method, organic coating is decyl mercaptan.In further example In property implementation method, organic coating is lauryl amine.In each implementation method, organic coating is characterised by that thickness range is for about 1nm- about 500nm.

In several implementation methods, platform unit also includes film, wherein the film is configured to block at least one sensing Device is in response to humidity change generation signal.In some embodiments, the film includes being selected from epoxy resin, silicones, polyamides The resin of polyimide resin, polyimide resin, poly- (p- xylylene) resin and combinations thereof.Every kind of possibility represents the present invention Single implementation method.In additional implementation method, film thickness scope is for about 1 μm-about 1000 μm.

According to an implementation method, platform unit is also provided and detects that volatility interested is organic using analyte sensor Compound (VOC), wherein the analyte sensor is configured to sensing absorption analyte thereon and in response to described Analyte generates electric signal.In another embodiment, platform unit also provides the volatilization of the disease in detection denoted object Property organic compound.In another implementation method again, platform unit also includes film, wherein the film is configured to blocking at least One sensor (for example, temperature, humidity and/or pressure sensor) is in response to VOC (VOC) interested Produce signal.

In each implementation method, platform unit includes that at least three include with similar or different organic coating cladding The sensor of metal nanoparticle, wherein three sensors include the pressure sensing being deposited in the substrate of substantial flexibility Device, temperature sensor and humidity sensor, wherein the pressure sensor be configured to sensing apply pressure thereon and In response to the pressing creation electric signal；The temperature sensor be configured in response to temperature change show it is described with organic The metamorphosis of the metal nanoparticle of coating cladding, and generate electric signal in response to the metamorphosis；The humidity is passed Sensor is configured in response to the metamorphosis that humidity change shows the metal nanoparticle of the organic coating cladding, and And generate electric signal in response to the metamorphosis.

In one embodiment, platform unit includes that at least three include with similar or different organic coating cladding The sensor of metal nanoparticle, wherein three sensors include the pressure sensing being deposited in the substrate of substantial flexibility Device, the temperature sensor being deposited in substantially rigid substrate and the humidity sensor being deposited in substantially rigid substrate Device, wherein the pressure sensor is configured to sensing applies pressure thereon and in response to the pressing creation telecommunications Number；The temperature sensor is configured in response to the metal nanoparticle that temperature change shows the organic coating cladding Metamorphosis, and in response to the metamorphosis generate electric signal；The humidity sensor is configured in response to humidity Change shows the metamorphosis of the metal nanoparticle of the organic coating cladding, and in response to metamorphosis life Into electric signal.In the exemplary embodiment, pressure sensor and temperature sensor are comprising with to humidity (for example, vapor) The organic coating of muting sensitivity.In another illustrative embodiments, pressure sensor and temperature sensor include film, described Film is configured to block the sensor in response to humidity change generation signal.

In other embodiments, at least one of platform unit sensor includes dual sensing sensitivity.At one In illustrative embodiments, the sensor comprising dual sensing sensitivity is deposited in substantial flexibility or rigid substrate Temperature and moisture sensors, wherein the sensor is configured in response to temperature change and humidity change shows and uses organic painting The metamorphosis of the metal nanoparticle of layer cladding and in response to the multiple different electric signals of metamorphosis generation.Another In one illustrative embodiments, the sensor comprising dual sensing sensitivity is deposited on the pressure in the substrate of substantial flexibility Power and humidity sensor, wherein the sensor is configured to sense the pressure that is applied thereto and in response to pressure life Into electric signal, and it is further configured to the form that humidity change shows the metal nanoparticle coated with organic coating Change and generate electric signal in response to the metamorphosis.In another exemplary implementation method again, comprising the spirit of dual sensing The sensor of sensitivity is deposited on the pressure and temperature sensor in the substrate of substantial flexibility, wherein the sensor is configured Into the pressure that is applied thereto of sensing and in response to the pressing creation electric signal, and it is further configured to show in response to temperature Spend the metamorphosis of the metal nanoparticle that change is coated with organic coating and generate electric signal in response to the metamorphosis.

In other illustrative embodiments, platform unit of the invention includes two sensors, one of sensor The dual-pressure and humidity sensor being deposited in the substrate of substantial flexibility, and another sensor is deposited on substantially Dual-pressure and temperature sensor in flexible substrate.

Skilled addressee readily understands that can be with corresponding to the signal of load, the temperature and/or humidity change of each The letter calculated after calibrating and/or measure before various measurements from dual sensor is used using algorithm well known by persons skilled in the art Extracted in number.

In some embodiments, humidity sensor includes metal nanoparticle continuous coated with organic coating and not Continuum.In one embodiment, the discontinuity zone is for about the space of 10nm- about 500nm including size range. In another implementation method, the discontinuity zone includes the space between about 3% and about 90%.

According to additional implementation method, platform unit of the invention is integrated on electronics or artificial skin surface.

From specific embodiment described below, the further embodiment and four corner of applicability of the present invention will be bright Aobvious.It is, however, to be understood that specific embodiment and specific embodiment are while the preferred embodiment of the present invention is indicated, only Be given as an example, because from this specific embodiment, variations and modifications within the spirit and scope of the present invention Will be apparent to those of ordinary skill in the art.

Brief description

Figure 1A -1B：(Figure 1A) changes into 39 DEG C in response to temperature from 23 DEG C, the Δ R/ of the sensor based on NTMBT-MCNP R_b.Illustration：The amplification of 35-39 DEG C of temperature province.(Figure 1B) in response to various relative humidity levels, based on NTMBT-MCNP's The Δ R/R of sensor_b。

Fig. 2：5 sensors based on MCNP of duplication are to the increased relative response of relative humidity level.

Fig. 3 A-3I：(Fig. 3 A) has the schematic illustration of the lax substrate of ETP-MCNP films.(Fig. 3 B) has ETP-MCNP The schematic illustration of the effect that the bending substrate of film and bending are spaced to ETP-MCNP.(Fig. 3 C-3E)：Relaxed state (figure 3C), it is bent upwards the photo of (Fig. 3 D) and the device being bent downwardly on the PET of (Fig. 3 E).The distance between electrode is for about 1mm. (Fig. 3 F) three-point bending measure during under the conditions of bearing strength test (■) and zero load stress (O), on PET based on ETP- Δ R/R of the sensor of MCNP in response to stretching_b.(Fig. 3 G) is during three-point bending is measured in bearing strength test (■) and zero load Under the conditions of stress (O), the sensor based on ETP-MCNP on PET is in response to the Δ R/R that compresses_b.Dotted line is represented to curve Linear fit, for all 4 curve R²In the range of 0.996-0.999.Response limit drops to tens Pa, for PET bases Bottom, 40Pa is test limit.The Δ R/ of the ETP-MCNP sensors (thick line) of (Fig. 3 H) load and zero load (unload) (fine rule) R_bCompared to the time.The load (0.75gr) and zero load, Δ R/R of (Fig. 3 I) in response to 12 cycles_bCompared to the time.

Fig. 4 A-4D：By increasing lotus stress () and off-loading stress () during three point bending test, based on DT-GNP's Sensor compresses the Δ R/R of PE substrates to (Fig. 4 A) stretching and (Fig. 4 B)_b.Response is linear and repeatable.(Fig. 4 C) is curved The resistance variations (resistance shift) of the sensor based on DT-MCNP caused by curved surface.Load starting is in grams. (Fig. 4 D) sensor to apply~repeatability of the response of 250Pa (- 0.5 gram) stress.

Fig. 5 A-5C：The FE-HRSEM images of ETP-MCNP layers of drop coating in 36 substrates.(Fig. 5 A) is used The image of the drop edge of SE detectors；(Fig. 5 B) uses the image of the drop centered of SE detectors.(Fig. 5 C) is detected using BSE The image of the drop centered of device.Layer-substrate interface is deep to, white dashed line ring (Fig. 5 B and 5C) rupture in mark.

Fig. 6 A-6G：Using SE detectors, at (Fig. 6 A)50th, (Fig. 6 B) 127th, (Fig. 6 C) PET125, (Fig. 6 D)B.131, (Fig. 6 E)36th, (Fig. 6 F)50 and (Fig. 6 G) PVC200 On ETP-MCGNP drop coatings layer edge magnification at high multiple FE-HRSEM images.

Fig. 7 A-7G：Using SE detectors, at (Fig. 7 A)50th, (Fig. 7 B) 127th, (Fig. 7 C) PET125, (Fig. 7 D)B.131, (Fig. 7 E)36th, (Fig. 7 F)50 and (Fig. 7 G) PVC200 On ETP-MCGNP drop coatings layer edge FE-HRSEM images.

Fig. 8 A-8G：Using SE detectors, at (Fig. 8 A)50th, (Fig. 8 B) 127th, (Fig. 8 C) PET125, (Fig. 8 D)B.131, (Fig. 8 E)36th, (Fig. 8 F)50 and (Fig. 8 G) PVC200 On ETP-MCNP drop coatings layer low power amplify FE-HRSEM images.

Fig. 9 A-9B：(Fig. 9 A) difference flexible substrates (50：◆；36：PET125：O；b.131：▲；127：□；50：★ and PVC200：) on ETP-MCNP films ΔR/R_bRelative to load, such as measured by three point bending test.(Fig. 9 B) is with the sensor with substrate of different nature Load sensitivity, as the function of Young's modulus, geometrical property and rotary inertia.

Figure 10 A-10B：For the following, Δ R/R_bCompared to load (bottom x- axles) and strain (top x- axles)：(figure 10A) undergo 200mg-lgr loadThe ETP-MCNP films (load sensitivity=0.31) deposited on 36；With (Figure 10 B) undergoes the ETP-MCNP films (load sensitivity=0.01) deposited on PET125 of the load of 200mg-10gr.

Figure 11 A-11B：The Δ R/R of the ETP-MCNP sensors (thick line) of (Figure 11 A) load and zero load (fine rule)_bCompare In the time.The load sensitivity of the sensor that (Figure 11 B) is produced in the substrate with different elastic characteristics is used as Young's modulus With the function of substrate thickness.Error line is 3 standard deviations of similar sensor, and dotted line represents the linear trend of result.

Figure 12 A-12C：(Figure 12 A) is spaced the sensor for manufacturing, load spirit using on electrode with 0.5mm, 1mm and 3mm The change of the resistance (right side y- axles) of sensitivity (left side y- axles) and sensor.Error line is 3 surveys being spaced for special electrodes The standard deviation of the sensor of examination.The load of (Figure 12 B) for identical electrodes structure and substrate when the width of substrate is changed is sensitive Degree change.Error line is to carry out 3 standard deviations of repetition to the identical sensor with specific dimensions.(Figure 12 C) is for difference MCNP parts (NTMBT：○；And ETP：) load sensitivity change.Dotted line represents the linear fit to curve, and error line is The 3-5 standard deviation of sensor.

Figure 13：Calibration factor (GF) value extracted from the linear fit of the relative response of sensor is compared to strain.Asterisk Result as herein described is represented, circle is from Farcau et al., ACSNano2011,5,7137-7143；Tsung-Ching etc. People, J.Disp.Tech.2009,5,206-215；Vossmeyer et al., Adv.Funct.Mater.2008,18,1611- 1616；With Herrmann et al., the GF values of Appl.Phys.Lett.2007,91,183105.Dotted line represents linear fit.

Figure 14 A-14B：(Figure 14 A) ETP-MCNP/The baseline electrical resistance of 127 sensors changes compared to bending Cycle-index.(Figure 14 B) Δ R/R_bCompared to the load after 1 (), 5,000 (Δs) and 10,000 (O) individual bend cycles.

Figure 15 A-15B：(Figure 15 A) after temperature changes into 39 DEG C from 23 DEG C, the biography based on ETP-MCNP in PET base The Δ R/R of sensor_b.Illustration：RH fluctuations during experiment.(Figure 15 B) is based on the sensor of ETP-MCNP to various RH levels ΔR/R_b.Dotted line represents R²=0.98 linear fit.Error line is the dozens of measurement point of the response under specific RH levels Standard deviation.Illustration：Temperature fluctuation during experiment.

Figure 16 A-16C：(Figure 16 A) Morse code alphabet and numeral.(Figure 16 B) coding has 36 μ m-thicks" LNBD " on the sensor based on ETP-MCNP of substrate.PET base of (Figure 16 C) coding with 125 μ m-thicks The sensor based on ETP-MCNP on " SOS ".Apply pressure using finger (estimated pressure is for about 1KPa).

Figure 17：Use different base (center PET base with side at the silica substrate) MCNP different with two kinds The schematic illustration of the Prototyping Platform for sensing humidity, RH and load of (NTMBT at center ETP and side).Across base The line at bottom represents metal electrode.

Figure 18 A-18D：The Δ R/R of the NTMBT-MCNP sensors for having hole in silica substrate_bCompared to (Figure 18 A) Relative humidity and (Figure 18 B) temperature.The Δ R/R of the ETP-MCNP sensors in silica substrate_bIt is relative compared to (Figure 18 C) Humidity and (Figure 18 D) temperature.

Figure 19 A-19B：The resistance of the flexible ETP-MCNP sensors in (Figure 19 A) PET base as 3%RH under (▲) and The function of the temperature of (O) under 20%RH.The RH fluctuations of plot and display on right side when temperature is changed.In (Figure 19 B) PET base Flexible ETP-MCNP sensors resistance as () at 21 DEG C, at 25 DEG C at (×) and 30 DEG C the %RH of (●) function. Drawing on right side describes the temperature fluctuation when RH conditions are changed.

Figure 20：The load different for 3 kinds, for the Calculation Plane of the ETP-MCNP sensors in PET base.Load 0： It is zero load；Load 1：3gr loads；With load 2：6gr loads.Measured by non-flexible ETP-MCNP and NTMBT-MCNP sensors Temperature and RH.Use the solver script calculating parameters in excel.

Figure 21 A-21C：(Figure 21 A) is of the invention to be usedThe signal of the exemplary platform of substrate and gold electrode Property diagram.(Figure 21 B) represents the resistance variations of the S1 and S2 when by sensor exposed to the temperature and relative humidities for changing Different Plane.The Δ R/R of (Figure 21 C) S3_bTo the pressure for applying.

Figure 22 A-22B：The schematic illustration of (Figure 22 A) three-point bending facility.The point marked by bottom arrow is represented thereon Place the static inclined beams of flexible substrates.Upper arrow represents the position for applying strain.(Figure 22 B) stretches the schematic figure of facility Show.Substrate is in " dog bone " form, and handle attaches to the wider portion of sample.Arrow represents the direction of the strain for applying.

Figure 23：The schematic illustration of three-point bending sample size.

Figure 24：The schematic illustration of three-point bending facility.Point #1 and point #2 are the static inclinations for placing flexible substrates thereon Beam.Point #3 is that the probe controlled using separate screw applies stressed place.The resistance of MCNP films is by drain electrode and source electricity Pole measures.

Specific embodiment

The invention provides a kind of modular matrix or platform unit for detecting pressure, temperature and humidity simultaneously.Especially Ground, there is provided herein it is a kind of for multifunction manual or electronic skin application including with low-power (<0.5V) operating based on The platform of the sensor of MCNP.

The present invention is based in part on following having now surprisingly been found that：Flexible sensor based on MCNP can have can be again Multiple elastic deformation measured value, wherein load sensitivity≤0.24gr.In addition, further disclose identical sensor technology can Environmental condition is sensed for being used for measurement temperature (being less than 1 DEG C) and humidity (being less than 1%RH) change with excellent sensitivity. It is previously unrecognized that can be used the sensor based on MCNP detects pressure, temperature and wet simultaneously on single platform unit Degree.Using the identical sensor technology that is integrated on single platform unit detect pressure, temperature and humidity ability relative to Prior art provides significant advantage.Sensor based on MCNP provides repeatable even after many times bend cycles Response so that they are conducive to long-term use.Another advantage of the present invention comes from has high spatial with a large amount of manufacturings The ability of the micro scale sensor of resolution ratio, so that they can be integrated in people in good restriction with controllable position In work or electronic skin.

In order to realize independent sensitivity of the single sensor to single required parameter, following manufacture can be applied to adjust：

I () is by using the substrate with different flexible and geometrical properties.For example, by using the base of substantial flexibility Bottom, sensor generation is mainly due to the electric signal of the power for applying rather than temperature and humidity change.Similarly, by using basic Upper rigid non-stretching substrate, sensor generation is mainly due to temperature and/or humidity changes and the electric signal of non-pressure.

(ii) by using the different organic coating of metal nanoparticle.For example, by using two short thiol linkers Used as cladding organic coating, response of the sensor to gaseous analytes (including vapor) can substantially be suppressed.By making With lengthening joint as cladding organic coating, the absorption to various gases can be obtained, thus in response to the group of encapsulated nanoparticles The expansion of part provides measurable electric signal.

(iii) by adding thin (~50 μ m-thick) polymer film as the top cover of sensor.For example, adding the top cover can be with Substantially suppress the sensing to humidity and/or VOC.Accordingly, it is considered to thin tectorial membrane will limit vapor with The metal nanoparticle coated with organic coating interacts.The top cover should be thin and possess good heat conduction and low-heat Capacitance characteristic, to ensure the quick and accurate response to temperature and/or pressure change.

(iv) by changing deposition parameter.For example, by using layer by layer deposition technology (Makishima et al., J.Non- Cryst.Sol.1973,12,35-45), the control of the sensing sensitivity to various analytes can be obtained.

V () deposits NP by under different humidity levels.Accordingly, it is considered to comprising the MCNP films with discontinuity zone Sensor provides Negative Acknowledgment in the positive response of offer after various analytes after being exposed to vapor.Do not connected by changing Pore volume in continuous region, can control the sensitivity to humidity (vapor).

(vi) by using measurement before calibration and/or measurement after algorithm compensation, can obtain to by single parameter (for example, Only temperature) or multiple parameters (temperature, humidity and load or strain) influence data extraction.For example, two to load or should Becoming the sensor with muting sensitivity can provide sensing to the respective change of temperature and humidity, while the 3rd flexible sensor is carried For the sensing to temperature, humidity and load or strain.Algorithm can be used to temperature of the compensation by the 3rd flexible sensor after measurement Degree and humidity change the signal for producing with the signal for making it possible to extract or separate load or strain generation by applying.Another In individual example, two sensors can be while sensing temperature and humidity, have different sensitivity to each parameter.Then, survey The mode penetrated within algorithm can be used to after amount calculates temperature and relative humidity.

Sensing platform unit based on MCNP of the invention is particularly suitable in artificial or electronic skin technology.The present invention Platform unit eliminate demand to the complicated integrating process of substantially different equipment, each equipment to humidity, temperature or Pressure sensitive.Sensing platform unit based on MCNP of the invention is had with using the cost of various deposition techniques (for example, spraying) A large amount of productions of effect are compatible.Pressure of the extra advantage from the wide scope that can be detected and measured by pressure sensor Power, it can be realized by depositing MCNP in the different base with various mechanical performances and geometric properties.Additionally, soft Property substrate on the non-normal-low pressure that fails to detect to hitherto known pressure sensor is provided using MCNP pressure sensors Measurement (Maenosono et al., J.of Nanopart.Res.2003,5,5-15).Another advantage of the sensor based on MCNP The ability that to be them operate under the low-voltage of~0.5V, and the requirement of hitherto known skin technology works in 5V or more relative superiority or inferiority. This low-voltage demand is promoted using mobile battery set forth herein the integrated of technology.

This invention therefore provides the sensing platform unit based on MCNP with excellent temperature and humidity sensitivity, institute Sensitivity is stated to make it possible to sense environmental condition.Sensing platform unit based on MCNP of the invention is additionally provided to the excellent of strain Different sensitivity so that it can act as " touch " sensor.Sensing platform unit based on MCNP can be in artificial or electronics skin Integrated in skin application.

Principle of the invention, platform unit provides the detection to pressure, temperature and/or humidity.In some embodiment party In formula, detected while platform unit is provided to pressure, temperature and humidity.Platform unit includes multiple sensors, each sensing Device includes multiple metal nanoparticles coated with organic coating.In some embodiments, each sensor is used comprising multiple The metal nanoparticle of different organic coating claddings.Suitable metal nanoparticle within the scope of the invention includes, but Be not limited to, Au, Ag, Ni, Co, Pt, Pd, Cu, Al and combinations thereof, including metal alloy is such as, but be not limited to Au/Ag, Au/Cu, Au/Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt/Rh, Ni/Co and Pt/Ni/Fe.Every kind of possibility represents of the invention Single implementation method.

The organic coating of metal nanoparticle includes single or multiple lift organic molecule.Suitable coating includes, but are not limited to Alkyl hydrosulfide --- for example with C₃-C₂₄The alkyl hydrosulfide of chain, aryl mercaptan, alkylaryl thiol, alkenyl mercaptan, alkynyl mercaptan, Cycloalkyl mercaptan, heterocyclic radical mercaptan, heteroaryl mercaptan, alkyl sulfide alkoxide, alkenyl mercaptan salt, alkynyl mercaptides, cycloalkyl mercaptan Salt, heterocyclic radical mercaptides, heteroaryl mercaptides, omega-functionalized alkanethiol salt, arene thiolate, (γ-mercaptopropyi) three Methoxy silane, dialkyl disulphides and combinations thereof.Every kind of possibility represents single implementation method of the invention.It is exemplary Organic coating include, but are not limited to 2- nitro -4- TRIFLUORO-METHYLs benzenethiol, 3- ethoxylated thiophenols, lauryl amine and last of the ten Heavenly stems sulphur Alcohol.Every kind of possibility represents single implementation method of the invention.In each implementation method, organic coating is characterised by thick Degree scope is for about 1nm- about 500nm.

Sensor comprising the metal nanoparticle coated with organic coating can synthesize as known in the art, example Such as, using two phase process (Brust et al., J.Chem.Soc.Chem.Commun., 1994,7,801), wherein making some improvement (Hostetler et al., Langmuir1998,14,17).In non-limiting examples, by AuCl₄ ^-From aqueous HAuCl₄·xH₂O Solution is transferred to toluene solution by consisting of phase-transferring agent TOAB.After organic phase is separated, to the mercaptan of solution excessive addition.Mercaptan: HAuCl₄·xH₂The mol ratio of O can be 1:1 and 10:Change between 1, this depends on the mercaptan for using.Carry out the process and be for Prepare the monodisperse liquor of the gold nano grain of average-size about 3-6nm.Exemplary program includes, but are not limited to, for Average-size is for about the gold nano grain of lauryl mercaptan and the butyl mercaptan cladding of 5nm, mercaptan:The mol ratio of Au is respectively 10:1 He 1:1.After strong stirring solution, large excess of reducing agent NaBH is added₄The aqueous solution.Reaction be continuously stirred at room temperature to It is few 3 hours, the dark brown solution of the Au nano particles to produce mercaptan to coat.The solution for obtaining is further in a rotary evaporator Solvent removal is carried out, ethanol is then used by and toluene is repeatedly washed.The gold nano grain coated with such as 2-mercaptobenzimidazole Can be synthesized by the gold nano grain of previously prepared hexyl mercaptan-cladding by part-exchange process.In typical reaction, mistake The mercaptan of amount, 2-mercaptobenzimidazole, solution of the gold nano grain that addition to hexyl mercaptan is coated in toluene.This solution is protected Lasting stirring a couple of days, to allow ligand transformations as much as possible.Received by extracting to be purified from free mercaptan part repeatedly Rice grain.Metal nanoparticle can have any required geometry, include, but not limited to cube, spheroid and ellipsoid Body geometry.Every kind of possibility represents single implementation method of the invention.

In some embodiments, multiple sensors include at least one pressure sensor, and it is configured to sensing and applies Pressure thereon and in response to the pressing creation electric signal.Principle of the invention, pressure sensor is substantially soft Property substrate on manufacture.Term " substrate of substantial flexibility " refers to as used herein to be configured in response to pressure bullet Property deformation substrate, wherein the deformation to apply amount of pressure it is proportional.In some embodiments, the deformation of substrate is produced The metamorphosis of the metal nanoparticle coated with organic coating.The metamorphosis of the metal nanoparticle coated with organic coating Or the displacement structure generation electric signal proportional to the amount of pressure for applying.In other embodiments, pressure sensor is configured Into the strain gauge that mechanical bias are transformed into electric signal.

The substrate of suitable substantial flexibility includes stretchable substrate as known in the art.Exemplary substrate bag Include, but be not limited to polymer, the polymer can be polyimides (for example), polyamide, polyimides (for example Polyethyleneimine), polyethylene, polyester (for examplePET, PEN), it is poly- Dimethyl siloxane, polyvinyl chloride (PVC), polystyrene etc..Every kind of possibility represents single implementation method of the invention. In one implementation method, substrate includes silica.In another embodiment, substrate includes Si rubber.By that will be formed The material of the substrate of substantial flexibility can be obtained from the material modification with high Young's modulus into the material with low Young's modulus Obtain the change of load sensitivity.Therefore consider that the substrate of substantial flexibility is capable of the load sensitivity of control pressure sensor.

The substrate of substantial flexibility can have any required geometry.It is substantially soft in rectangular geometry The width range of the substrate of property is for about between 0.01-10cm.The thickness of substrate can be adjusted further, typically in about 20-500 In the range of μm.Regulation by changing the width of sensor base to provide to load sensitivity of the invention.In addition, of the invention Regulation to calibration factor is provided by adjusting substrate thickness.Accordingly, it is considered to pass through to change the geometrical property of substrate, can obtain Obtain required load sensitivity and strain calibration factor.

Platform unit of the invention also includes at least one temperature and/or humidity sensor, and it is configured in response to temperature Degree change and/or humidity change show the metamorphosis of the metal nanoparticle coated with organic coating.This metamorphosis is right The electric signal of response generation is transformed into afterwards.Therefore, the electric signal changes to humidity and/or temperature change is proportional.

In some embodiments, temperature and/or humidity sensor are substantially rigid as described herein or substantially Manufactured in flexible substrate.Typically, temperature and/or humidity sensor are manufactured in substantially rigid substrate.In the present invention In the range of suitable substantially rigid substrate include, but are not limited to metal, insulator, semiconductor, semimetal and its group Close.Every kind of possibility represents single implementation method of the invention.In the exemplary embodiment, substantially rigid substrate bag Include the silica on silicon chip.In another illustrative embodiments, substantially rigid substrate is comprising substantially rigid Polymer.In still another example implementation method, substantially rigid substrate includes tin indium oxide.

In each implementation method, pressure of the invention and/or temperature sensor are coated with film.Original of the invention Reason, the film is configured to occluding pressure and/or temperature sensor response in humidity change generation signal.In the scope of the present invention The non-limiting examples of interior film include epoxy resin film, silicone resin film, polyamide resin (such as nylon and aramid fiber resin), Polyimide resin film, poly- (p- xylylene) resin film is (for example) and combinations thereof.Every kind of possibility generation Table single implementation method of the invention.Typically, occluding pressure and/or temperature sensor response is configured to change in humidity The thickness range for generating the film of signal is for about 1-1000 μm.

According to some aspects and implementation method, platform unit includes that at least three is following comprising being coated with organic coating The sensor of metal nanoparticle：

I () is deposited on the pressure sensor in the substrate of substantial flexibility, wherein the pressure sensor is configured to sense The pressure that is applied thereto of survey and in response to the pressing creation electric signal；

(ii) temperature sensor in substantially rigid substrate is deposited on, wherein the temperature sensor is configured to ring The metamorphosis of the metal nanoparticle coated with organic coating should be shown in temperature change, and in response to the metamorphosis Generation electric signal；With

(iii) humidity sensor in substantially rigid substrate is deposited on, wherein the humidity sensor is configured to The metamorphosis of the metal nanoparticle coated with organic coating is shown in response to humidity change, and is become in response to the form Metaplasia is into electric signal.

In some embodiments, temperature and moisture sensors be configured in response to temperature change or humidity change it is every One independent metamorphosis for showing the metal nanoparticle coated with organic coating.

According to some aspects and implementation method, humidity sensor includes the conducting metal nano particle coated with organic coating Both continuously and discontinuously region.In one embodiment, discontinuity zone is for about 10nm- about 500nm comprising size range Space, the percentage range of its void is for about between 3% and about 90%.

In some embodiments, platform unit includes multiple conducting elements (such as electrode), and it is coupled to each biography Sensor, so that the signal generated by sensor can be measured.Conducting element can include being separated by source-leak Source electrode and drain electrode.Conducting element may further include gate electrode, and wherein electric signal can indicate the influence in gate voltage Some properties (metamorphosis of such as encapsulated nanoparticles) of lower encapsulated nanoparticles.

Conducting element can include metal such as Au, Ag or Pt electrode, and further can be connected by interconnection patch. The distance between adjacent electrode limits sensing area.Therefore, the different configurations of the electrode in platform unit can be as in this area Known manufacture.Typically, the distance between adjacent electrode scope is for about between 0.01-5mm in each sensor.In some realities Apply in mode, metal nanoparticle casts (cast) in the multiple interdigital electrodes in substantial flexibility or rigid substrate.

Principle of the invention, the electric signal generated by pressure, temperature or humidity sensor can include sensor Any one or more in electrical conductivity, resistance, impedance, electric capacity, inductance or optical property.In some embodiments, electric signal Produced by the expansion for changing the component of encapsulated nanoparticles in response to pressure, temperature or humidity.As used herein, art Language " expansion " refer to encapsulated nanoparticles component between average grain distance increase.In other embodiments, electric signal Produced by the aggregation for changing the component of encapsulated nanoparticles in response to pressure, temperature or humidity.As used herein, art Language " aggregation " refer to encapsulated nanoparticles component between average grain distance reduction.

Sensor signal can be detected by detection means.Suitable detection means is included to any one in following items Or the device of the sensitive of multiple：Resistance, conductance, alternating current (AC), frequency, electric capacity, impedance, inductance, mobility, potential, Optical property and voltage threshold.Every kind of possibility represents single implementation method of the invention.In additional implementation method, inspection Survey device include to the expansion of encapsulated nanoparticles or the sensitive device of aggregation and in following items any one or more The device of sensitive：Optical signalling (being detected for example, by elliptical polarizer), fluorescence, chemiluminescence, luminescence generated by light (photophorescence), bending, surface acoustic wave, piezoelectricity etc..Every kind of possibility represents single implementation method of the invention. The electric signal for measuring may be displayed on display or transmit to main frame.

Sensor of the invention can be configured as any one in polytype electronic device, included, but not limited to Capacitance sensor, resistance sensor, resistive chemisensor, impedance transducer, field effect transistor sensing device etc., or it Combination.Every kind of possibility represents single implementation method of the invention.In non-limiting examples, sensor of the invention It is configured as resistive chemisensor (that is, chemiresistor).In one embodiment, sensor of the invention not by It is configured to impedance transducer.

The sensor of the metal nanoparticle comprising multiple organic coating cladding can use as known in the art many The technology of kind is formed in flexibility or rigidity substrate.Example technique includes, but not limited to

I () is by drop coating, spin coating, the spraying technology similar with other from solution random deposition.Every kind of possibility represents this The single implementation method of invention.

(ii) electric-field enhancing or interaction of molecules induction from liquid deposition.Every kind of possibility represents of the invention independent Implementation method.

(iii) Langmuir-Blodgett or Langmuir-Schaefer technologies.Every kind of possibility represents of the invention Single implementation method.

(iv) soft lithography, such as micro-contact printing (mCP), duplicating molded (replica molding), hair The micro- molding of tubule (MIMIC) and micrometastasis molding (mTM).Every kind of possibility represents single implementation method of the invention.

Various groups of (v) Langmuir-Blodgett or Langmuir-Schaefer methods and soft lithography Close.Every kind of possibility represents single implementation method of the invention.

(vi) using specifies the ink-jet printer for printed form electronic product to be printed in solid-state or flexible substrates.

Present invention also contemplates that the sensor with dual sensing sensitivity, such as dual-temperature and pressure sensor, dual Temperature and moisture sensors and/or dual-pressure and humidity sensor.Every kind of possibility represents single embodiment party of the invention Formula.

The non-limiting examples of the platform unit including dual sensor include such platform unit, and it includes three biographies Sensor, two of which sensor is deposited on dual-temperature and humidity sensor in the substrate of substantial flexibility, the 3rd pressure Force snesor is deposited in the substrate of substantial flexibility.Consider the selection of substrate is used for changing sensor to load, temperature and/ Or the sensitivity of humidity change.The additional non-limiting examples of the platform unit including dual sensor include such platform Unit, it includes two sensors, and one of sensor is deposited on dual-pressure in the substrate of substantial flexibility and wet Degree sensor, and another sensor is deposited on the pressure and temperature sensor in the substrate of substantial flexibility.This area Technical staff be readily appreciated that using measurement before calibration, measurement after calculate or its combine extract by each parameter (temperature, humidity or Pressure) generation signal.

The arrangement of multiple sensors can be carried out as known in the art in platform unit.Nonrestrictive arrangement includes passing Sensor matrix (row and column), it includes multiple sensors, such as sensor between 2 and 20, wherein each sensor independence Ground generates electric signal in response to pressure, temperature and/or humidity.Each sensor is included with different or similar organic coating bags The metal nanoparticle for covering and different or similar substrates.

According to some aspects and implementation method, sensor of the invention is coated with film.In some embodiments, the film For the metal nanoparticle coated with organic coating provides the protection to physical hazard, scratch and oxidation.Coating can be by this Well known method is carried out in field, such as, but is not limited to, spin coating etc..The film can be permeable or impermeable to water, this Depending on required application.The film can conduct heat or completely cut off sensor and exterior temperature change.In some implementation methods In, the film includes polycyclic aromatic hydrocarbon (PAH).In other embodiments, the film includes carbon coating, carbon nitride coatings, thermoplastic Property resin, silicate coating or any other suitable coating as known in the art.Typically, the thickness range of the film is About 10 μm of about 0.001-.

According to various aspects and implementation method, platform unit further provides organic to volatility using analyte sensor The detection of compound (analyte), wherein the analyte sensor is configured to sense analyte and the sound for adsorbing thereon Analyte generation electric signal described in Ying Yu.Accordingly, it is considered to platform unit will further provide it is organic to volatility in surrounding environment The presence of compound and the detection of concentration.In some embodiments, VOC is the disease in denoted object Or the biomarker of illness.

Platform unit of the invention can be used for artificial and/or electronic skin application, and application requirement production is extensive to be passed Sensor array, the large-scale sensor array can sense load, relatively wet with resolution ratio high and short response time Degree and temperature.Artificial and/or electronic skin can be integrated in medical prosthesis and robot industry.Other application includes, but It is not limited to, is used for following the trail of the load (such as harbour employee (harbor employees)) of their carryings and measuring him by individuality Physical responses --- including body temperature and humidity --- application；With for covering the application of the engine of automobile and aircraft, It can be configured to setting carries out alarm once detecting too high temperature or pressure and/or the early formation of crackle occur.

When using herein and in attached claims, singulative " one ", " one kind " and " described " include Plural thing, unless context is additionally explicitly pointed out.Thus, for example, including when referring to " organic coating " multiple such Organic coating and its equivalent well known by persons skilled in the art, etc..It should be noted that term " and " or term "or" it is general with Its implication for including "and/or" is used, unless context is additionally explicitly pointed out.

Propose the following examples more fully to illustrate some embodiments of the present invention.However, they determine Should not be construed as limited to obvious scope of the invention.Without departing from the scope of the invention, people in the art Member is easily envisaged that many changes and modifications of principle disclosed herein.

Embodiment

Material and method

The synthesis of MCNP：

Chlorauride (III) trihydrate (HAuCl₄·3H₂O), ammonium bromide and tetraoctyl ammonium bromide (TOAB), sodium borohydride, 3- ethyoxyls Benzenethiol (ETP), decyl mercaptan (DT) and 2- nitros -4- TRIFLUORO-METHYLs benzenethiol (NTMBT) are purchased from Sigma-Aldrich.It is all Reagent is AG, and is used by sample.Spherical gold nano grain (AuNPs；Diameter 3-6nm) such as Peng et al., Nature Nanotech.2009,4,669-673；With Dovgolevsky et al., J.Phys.Chem.C.2010,114, Synthesis described in 14042-14049, their each contents are totally integrating herein.In short, by the solution of HAuCl4 In agitating solution of the addition to TOAB in toluene.After stirring 10min, lower floor's water phase is removed.Then by organic ligand and boron hydrogen Change sodium to add into toluene phase.Under ice temperature after 3 hours, remove lower floor's water phase and toluene then evaporated by rotary evaporation Phase.After being washed with cold ethanol first, solution is kept for 18 hours at 5 DEG C, until realizing complete submergence.Filter crineous precipitation Thing is simultaneously washed with ethanol.

Sensor is manufactured：

Electrode deposition is in different isolation substrates (table 1).Electrode is prepared using silver paste (Mouser Electronics). Interval between electrode in all experiments of the inspection substrate to the effect of load sensitivity is typically 1mm.Using having 0.5th, 1 printed electrode with the similar of the variable interval of 3mm, so as to the effect at the interval between inspecting electrode.From with bending in fact Stretched on " dog bone " sample for testing the cutting of identical substrate.Electrode, electrode are prepared in a similar way using silver paste Between at intervals of 1mm.Substrate is available from DuPont (GADOT is retail trader).Flexibility is cast in by by 2 μ l MCNP in solution Flexible sensor is prepared on substrate/electrode.

MCNP layers of Morphological characterization：

The micro-structural and morphology of MCNP films pass through Flied emission high resolution scanning electron microscope (Carl Zeiss Ultra Plus FE-HRSEM) characterize.FE-HRSEM analyses are carried out using two kinds of main detectors：Secondary electron (SE) is examined Survey device and back scattered electron (BSE) detector.SE detectors provide the high-resolution imaging on surface.BSE detectors provide work It is the picture contrast and surface topography of the function of element composition.

Additionally by rapping formula AFM (AFM), (Dimension3100 is furnished with the morphology of MCNP films Nanoscope IIIa controllers, Veeco Instruments Inc.) check, the microscope is equipped with 100 × 100 μm²Sweep Retouch instrument.Using specified resonant frequency be 160kHz and spring constant is the silicon cantilever (NSCl of 5N/m₄/AlBs,MikroMasch, Estonia).All images are shot with the sweep speed of 1-2Hz and 512 × 512 pixel resolution.

The facility of bend test：

Apply the constant strain of 1.5mm/sec using MARK10ESM301 electrokinetic tests platform.For bending facility (figure 22A), indicated to apply stress by upper beam by upper arrow, underbeam is used as support beam.Under the stress/pressure/force for applying, base Bottom is bent.Then, make it is outer (on) surface through compressed, while interior (under) surface undergoes expansion.Manufactured by by Mark10USA Advanced Digital FORCE GAUGE measurement power.

The facility of tension test：

Apply strain/power between two metal handles on " dog bone " sample illustrated in Figure 22 B.Arrow is represented and drawn The direction stretched.Applied between the metal handle of wider portion of sample is attached to using MARK10ESM301 electrokinetic tests platform The constant strain of 1.5mm/sec, and there is the narrower portion in sample in most of strain.By what is manufactured by Mark10USA Advanced Digital FORCE GAUGE measure power.

The manufacture of integrated Pressure/Temperature/humidity sensor：

By by the aliquot drop coating of MCNP solution by 24 pairs with 1000nm SiO₂Au electricity on the silicon chip of film Manufactured based on SiO in the interdigital electrode of pole (5 μm of 25 μm of intervals between width and adjacent electrode) composition₂MCNP layers in substrate Humidity or temperature sensor.Between those sensors, flexible ETP-MCNP layers (Figure 17) in PET base is placed.On PET Electrode silk-screen printing (mash printed) is carried out by CPC Hi Technologies Ltd., at intervals of 1mm.

Evaluation temperature and the facility of relative humidity sensing experiment：

20 sensors are arranged on the PTFE circuit boards of customization.The circuit board is arranged on volume and is less than 300cm³'s In stainless steel test cabinet.In order to control relative humidity level (5-60%RH), from the commercially available nitrogen hair equipped with nitrogen purification instrument The purifying dry nitrogen (99.9999%) of raw device (N-30, On Site Gas Systems, USA) is as carrier gas.By drying nitrogen Mix with the humidified air generated by the humidifier module of system.Controlled temperature is produced by the temperature controller for customizing.Pass through Monitoring MCNP and environmental sensor (RH, temperature) are carried out to the response of the different relative humidity and temperature levels that are generated by system Sensing experiment.

Around during environment sensing experiment (table 3-4 and Figure 20), carry out to MCNP and environmental sensor (RH, temperature and Load cells) monitoring to the response of indoor difference relative humidity and temperature levels, it is simultaneously used in the sensor of test The power of upper applying.Carry out phase using by customizing the programme controlled Keithleydatalogger devices (model 2701DMM) of Labview Resistance readings are obtained from sensor array after ground, and voltage readings are obtained from environmental sensor.

Pressure sensor based on MCNP：

Sensor is manufactured in polyethylene (PE) substrate.Evaporated by shadow mask by by 20nm/200nm Ti/Au layers To be formed in substrate between 10 couples of 4.5mm interdigital (ID) electrodes wide, electrode at intervals of 100 μm.By drop coating representativeness MCNP The aliquot of solution prepares chemiresistor.Homemade three-point bending system is used in probe station.Under the power for applying, The beam for undergoing three-point bend test is bent downwardly, as being schematically illustrated in Figure 24.Then it is outer (on) surface through compressed, and Interior (under) surface is in tension.According to following equation, stress (or compression) can be calculated by the sample skew for measuring：

For rectangle sample (Figure 23), rotary inertia (I) is：

Surface area (A) is：

A=20mm²

The pressure (P) of applying is：

Wherein E is Young's modulus, and δ is the skew at sample center.For example, when using polyethylene as substrate, δ_{It is minimum} =0.075mm, Young's modulus is 500MPa, and the pressure of each deviant is：

P=0.032 δ

Using the minimum measurement deviant of 0.075mm, sensor undergoes the load of 0.24gr：

P（δ=0.075mm)=2.410^-3N=0.24gr

And the stress (σ) of the calculating for obtaining is：

The probe station for being connected to device analysis instrument (Agilent B1500A) is used for being based on during collecting bending and stretching The electric signal of the pressure sensor of MCNP.Measured under the constant voltage of 0.5V as the resistance of the function of time.

Embodiment 1：Sensing temperature and humidity

Check in the possibility for touching integrated temperature and humidity ability in platform based on MCNP.For this purpose, will Nitro -4- TRIFLUORO-METHYLs benzenethiol (NTMBT) MCNP sensors are placed in the vacuum chamber with controllable environment.With side progressively Formula changes temperature or relative humidity (RH), and monitors corresponding Δ R/R_b.Figure 1A gives the Δ of the sensor when temperature is raised R/R_b。ΔR/R_bIt is linear, and often increases by 1.33 DEG C of temperature reduction 1%, this causes this sensor sensitive enough to monitor Temperature fluctuation in surrounding environment.The spirit of amplification sensor of the display based on NTMBT-MCNP in 35-39 DEG C of temperature scenario Sensitivity is sufficiently high, and as low as 1 DEG C fluctuation or the artificial or electronic skin people that nearby thermal source is present can be accurately detected so as to serve as Thermometer body, without touching object.The ability of sensor-detected temperature is further using being deposited on several slides --- Including200 μ m-thicks and the PVC slides with much bigger thickness --- on NP films prove.All devices show Very strong response to variation of ambient temperature is shown：Used as to 1 DEG C of response of temperature change, baseline electrical resistance change turns to 1%.Under One step, in identical4 devices are manufactured on slide, and is connected to electric resistance measuring apparatus.Duplicate measurements institute There are four resistance values, cycle time is~1 second.These devices are placed face down on non-flexible platform.Once hot object (people Hand) close to each (or all) sensor proximity, baseline electrical resistance changes to relatively low value.No matter hot object when approaching device (1-5cm), this phenomenon is repeated.After hot object is removed, this effect is reversible, and when object is in identical with sensor At a temperature of when do not observe this effect.The response time of sensor is for about approximately 1 second, i.e. be placed in sensor proximity in staff About 1 second afterwards, it was observed that the significant changes of baseline electrical resistance.In 15 seconds, for all 4 sensors, resistance change~4- 6%.Therefore, sensor of the invention and platform unit are very sensitive to temperature and heat, and can in the short term sense and connect Hot object closely near them.Unit temp and close to the temperature difference between the staff near it be~15 DEG C.

Figure 1B is based on NTMBT MCNP in being displayed in the humidity regions (5-60%RH) being present in most of environmental applications Sensor relative response.The amplitude of relative response is Linear proportional with the RH levels of measurement, and sensitivity drops to list Individual RH percentages.Replicate sensor and show good uniformity (Fig. 2) in response to different RH levels.Specifically, testing humidity is passed 5 of sensor replicate to evaluate the repeatability of production and performance.It is right that the sensor based on MCNP of all 5 duplications shows The substantially the same response amplitude of the RH levels of all tests, has linear dependence to RH levels.These results are highlighted Temperature and moisture sensors are produced and are integrated into based on NTMBT MCNP sensors the part of artificial or electronic skin application Possibility.

Embodiment 2：The influence of stretching and bending to flexible MCNP sensors

Under bending and stretching condition, checked at flexible PET (PET) by three-point bend test The pressure sensor of the gold nano grain of use 3- ethoxylated thiophenols part (ETP-MCNP) cladding in substrate.All experiments exist Carried out under 20 DEG C ± 1 DEG C of room temperature and 50% ± 3% relative humidity (RH) level.Fig. 3 F-3G give ETP- in PET base The load of MCNP strain transducers and zero load curve.When in one case stretching and compress ETP- in another case During MCNP films, relative resistance response (Δ R/R is obtained_b, wherein R_bIt is the baseline electrical resistance for not applying load on a sensor, Δ R is R_bAnd the resistance variations between the resistance when load is applied on a sensor).The bent horizontal of PET base is being altered in steps Afterwards, the positive change of resistance or negative change are linear.When ETP-MCNP films to be placed in the top side of PET base, bending substrate is led The compression of ETP-MCNP films is caused, so that ETP-MCGNP is closer proximity to each other and allows tunnel current higher.Therefore, surveyed Measure the reduction (Fig. 3 E and 3G) of resistance.When ETP-GNP films to be placed in the bottom side of PET base, bending substrate increased adjacent The distance between ETP-GNP, causes less tunnel current, and therefore, measurement resistance increases (Fig. 3 D and 3F).Fig. 3 H show ETP-MCNP sensors response after with time continuous compression.Load and it is zero load represented by thick line, and load variations Represented by fine rule.Sensor response closely follows load curve.Peak load is for about 6gr, and respective response is~20%.Separately Outward, load-baseline electrical resistance of sensor is similar after the zero load cycle.Fig. 3 I show that ETP-MCNP sensors are worked as and undergo 12 The high performance reproducibility of response when individual load (0.75gr) and zero load cycle to stretching.As seen in FIG., to the phase of load It is for about 5% to electrical response change.The response of sensor is repeatable, and relative standard deviation's (5% ± 0.075%) of response is 1.5%, the relative standard deviation of baseline electrical resistance value is~2%.In grams, the wherein load of 1gr is equivalent to about unit demand 0.01N。

The gold nano grain coated using the use decyl mercaptan (DT-MCNP) in flexible polyethylene (PE) substrate is similar to Result.DT-MCNP films are bent and stretched.Fig. 4 A-4B give polyethylene (PE) base for undergoing three-point bend test The load and zero load curve of the DT-MCNP strain transducers on bottom.Relative resistance sensing signal (Δ R/R_b) be displayed in progressively Decrease or increase the linear positive or negative change of resistance after the bent horizontal of PE substrates.It is placed on the top side of PE when by DT-MCNP films When, bending substrate compression DT-MCNP films thus reduce the distance between adjacent DT-MCNP, thus allow tunnel higher The reduction (Fig. 4 B) of electric current and measurement resistance.When DT-MCNP films are placed on the bottom side of PE, bending substrate increased adjacent The distance between DT-MCNP, causes less tunnel current, and therefore, increased measurement resistance (Fig. 4 A).In the load of Fig. 4 A Obvious hysteresis is there is and zero load curve between.Response limit drops to tens of Pa, and 20Pa is for this specific substrate Test limit.In current facility, 20Pa is equal to~and 400mg is placed in 20mm²Area on, as seen in Fig. 4 C, by application The load step of about 0.24gr, obtains the resistance variations more than 1 Κ Ω.Weight with load on sensor increases, and noise subtracts It is small.However, being readily detected as little as 0.25 gram of weight loading on noise level.The stretching of identical sensor causes similar Load inserts (inset), but the positive change with resistance.Fig. 4 D are shown when the weight that 250Pa is carried out on DT-MCNP sensors The repeatability responded when the load of combined stress and zero load cycle.The signal to noise ratio being computed of response is for about 38, the response time Less than 1 second.

In order to assess the scope of load sensitivity, similar survey is carried out in the several substrates with different elastic propertys Amount.Three-point bending calculating is carried out having as follows in several substrates of different elastic propertys (different Young's modulus)：PDMS (Young's modulus is 360-870KPa；PE (Young's modulus is~500MPa)；SiO₂(glass；Young's modulus is~70GPa)；With Silicon rubber (Young's modulus is~75KPa).For minimum load assessment, the minimum measurement deviant of 0.075mm, sensor are used Undergo the load of 0.24gr in PE substrates.It is identical in order to realize when using PDMS as substrate under the same test conditions The skew (skew with strain and resistance change is proportional) of level, it is necessary to make sensor undergo the only load of 0.24mg, and because This is up to relatively low test limit.When substrate is used glass as, the survey of the stress value compared with PE substrates can be obtained Amount, while keeping similar strain level.Therefore, the deviant of 0.525mm, DT-MCNP-SiO are used₂Platform will need to undergo The load of 238gr is reaching the similar shift reached during with the load for undergoing 1.7gr when DT-MCNP-PE platforms.

When using PDMS as substrate, sensor is sensitive to the load of 0.24mg.Obtained with for the DT-MCNP on PE The sensitivity (1.7gr) for obtaining is compared, glass (SiO₂) on DT-MCNP sensitivity to more high load capacity (238gr) is provided.When making During with Si rubber as substrate (DT-MCNP-Si rubber platforms), the test limit being computed is lower than DT-MCNP-PE platform 8 times.

Propose the adjustable load sensor based on ETP-MCNP layers for casting on a flexible substrate.Repetition in Fig. 3 I The substandard difference and high s/n ratio of the signal output of load ensure the repeatable measurement of sensor.When bending increased nano particle Between apart from when, between load and zero load sensing curve exist offset.Do not constrained by any theoretical or mechanism of action, This skew can be attributed to ETP-MCNP layers of irreversible change (for example, forming crackle；Olichwer et al., ACS ) or MCNP displacements Appl.Mater.Interf.2012,4,6151-6161.

Embodiment 3：Influence of the substrate to MCNP layers of morphology and to associated sensed property

The relative response of sensor is directly proportional (for specific bending facility) to skew.Therefore, it is larger inclined when introducing During shifting, the response of flexible sensor increases.Because big skew can cause to flexible substrates and to both MCNP layers no The load sensitivity scope, it is necessary to certain is reversibly changed.In this way, the measurable height of thick substrate with high Young's modulus is used Load, and use the measurable Smaller load of thin substrate with low Young's modulus.

By the way that ETP-MCNP films to be deposited in following substrate the property to seek substrate and the load biography based on MCNP Relation between sensor：I () has the substrate of similar composition (for example, identical polymer) but different-thickness；(ii) has The substrate (for example, substrate of 50 μ m-thicks) of difference composition (for example, different polymer) but comparable thickness.Flexible substrates and they Property be listed in Table 1.

The MCNP/ substrate sensors of the manufacture of table 1.

^(a)Load sensitivity：The relative resistance change of per unit load variations.

It is different with AFM (AFM) research by Flied emission high resolution scanning electron microscope (FE-HRSEM) The surface morphology of the ETP-MCNP films in substrate.Fig. 5 A-5C showThe surface shape of the ETP-MCNP films on 36 State.Fig. 5 A show the edge of the film under low multiplication factor (× 200).Deposited in substrate by by GNP solution drop coatings These layers.It can be seen that " coffee ring " sample surface texture of a diameter of hundreds of microns formed during deposition process of rupture.In liquid The center (left side of Fig. 5 A and Fig. 5 B-5C) of drop forms continuous film.In the center of drop, thickness degree is in 400-900nm Between change (as pass through AFM Estimation and Measurements).Larger multiplication factor (× 30,000) to the center discloses small " bubble Sample " structure, its part has the center (Fig. 5 B-5C) of rupture.With those crackle (figures of back scattered electron (BSE) analytical control Dark color compared with other regions on ETP-MCNP films 5C) is shown, deep these crackles exposure of this tens nanometers of prompting Layer-substrate-interface.Fig. 6 A-6G show (Fig. 6 A)50th, (Fig. 6 B)127th, (Fig. 6 C) PET125, (Fig. 6 D) B.131, (Fig. 6 E)36th, (Fig. 6 F)50 and (Fig. 6 G) PVC200 ETP-GNP layers of edge (its pass through drop " coffee ring " sample surface texture sign).These figures high-amplification-factor (× 30, 000) deep torn grain for reaching polymeric substrates is disclosed.These crackles cause the non-conductive property at layer edge.In smaller multiplication factor The image of lower shooting shows that the phenomenon is extensive and occurs (Fig. 7 A-7G) for various substrates.

Fig. 8 A-8G show the center of the deposition drop of the ETP-MCNP in various substrates.ETP-MCNP layers different There is similar surface morphology in substrate.In addition to PVC200, all substrates show the continuous film of height, different substrates Cause " bubble sample " structure of different densities.For PVC200, crackle occurs on whole layer.Even so, it was observed that continuous Surface region (Fig. 8 G).Not by any theoretical or mechanism of action constraint, " coffee ring " and " water in the interior section of layer The morphology of bubble " can by drying when drop in capillary flow explain (Deegan et al., Nature1997,389,827- 828；Deegan et al., Phys.Rev.E2000,62,756-765；And Deegan, Phys.Rev.E2000,6,475-485). The difference of " bubble " density can be attributed to the different adhesivenesses between ETP-MCNP solution and different base, and it causes drop again Drying process during different capillary force.Different base is firmly believed for the similar morphology that most of substrates for using are obtained Mainly being influenceed without being influenceed by ETP-MCNP layers of Morphological Differences by substrate between upper ETP-MCNP layers.

Fig. 9 A show the response of the pressure sensor measured by three-point bend test.All experiments are carried out, while will Room temperature is maintained at 20 DEG C ± 1 DEG C and relative humidity level is maintained at 50% ± 3%.Carry out electrical measurement using silver electrode, electrode it Between at intervals of 1mm.Sensor is tested under a series of loads (0.5-3.5gr), and average response is computed repeatedly from 3-5 (ΔR/R_b).Response is linearly increasing (Fig. 9 A) with the increase of load.Fig. 9 B are shown with the biography with substrate of different nature The load sensitivity of sensor, its as Young's modulus, geometrical property and rotary inertia function.Slope indicate load sensitivity according to Rely the machinery and geometric properties in substrate.Aobvious with specific load is applied in the ETP-MCNP layers of similar different substrate of coating Obvious response difference is shown.For example, being coated with ETP-MCNP filmsB.131 applying is gone up to be equal to The response (~3%) that the load of 0.9gr is produced is less than using36 used as the base coated with similar ETP-MCNP films The response (~27%) that bottom obtains.This species diversity can be attributed toThe larger elasticity of 36 substrates.Do not receive any theory Or the constraint of mechanism of action, The larger elasticity of 36 substrates can cause larger point between the ETP-MCNP of sensed layer From (during when bottom side of the ETP-MCNP films in substrate；Alvares et al., Procedia Eng.2011,25,1349-1352).Phase The load sensitivity of sensor is provided compared to the slope of load to resistance, this depends on Young's modulus E, and depending on such as Lower shown rotary inertia I：

Wherein b is the width (its is essentially similar in all substrates for using) of substrate, and h is the thickness of substrate. The sensitivity of sensor, the relation between load and floor parameter are provided by following equation：

Wherein Δ Ρ is load variations.Fig. 9 B show the average load sensitivity of substrate, its as substrate Young mould The function of amount and rotary inertia.Load sensitivity is clearly dependent on base property.Specifically, in the thickness and its Young of substrate There is correlation between modulus and load sensitivity, wherein the relatively thin substrate with relatively low Young's modulus has load spirit higher Sensitivity.Error line in Fig. 9 B represents the 3-5 standard deviation of similar substrate.For most of substrates, standard deviation is sensitiveer than load Degree small an order of magnitude of average value.

In order to assess the scope of load sensitivity, two kinds of sensor is checked under various loads：I () existsThe ETP-MCNP films (load sensitivity=0.31) deposited on 36, it undergoes 200mg-1gr loads；(ii) exists The ETP-MCNP films (load sensitivity=0.01) deposited on PET125, it undergoes 200mg-10gr loads.Figure 10 A-10B show Δ R/R_bCompared to load (bottom x- axles) and strain (top x- axles).By changing the type of substrate, sensor is obtained To specific load and the change of the response of strain.When the high response to low strain dynamic and load is required, it is possible to use with height The sensor of load sensitivity, for example36, it has~15% response (figure to 1gr loads and 0.07% strain 10A).When improved strain and load range is applied, it is possible to use the sensor with less load sensitivity, for example PET125, it can sense up to 10gr loads and 0.25% strain (Figure 10 B).

The tensile property of sensor of the test based on ETP-MCNP.Prepare " dog bone " sample (Figure 11 A；Illustration) and Stretched on " Mark10 " electric test bench, while measuring power in dynamometer is supplemented.Stretching sample --- while being applied to Power in the range of the linear elasticity of the substrate of load-deformation curve, it then follows Hocks laws：

σ=ε E

Wherein σ be apply power divided by cross-sectional area, ε is the strain of sample, and E is Young's modulus.In this facility, The width of all the sensors is substantially identical.Therefore, load sensitivity is expressed as：

Wherein h is substrate thickness.Figure 11 A show the ETP- under the continuously elongated load with the time and zero load (fine rule) MCNP sensors respond (thick line).The response of sensor closely follows load curve.Peak load is for about 150gr, with~ 27% corresponding response.Load-baseline electrical resistance of sensor is similar after the zero load cycle.Figure 11 B are given as substrate Young's modulus and thickness function load sensitivity.Error line is 3 standard deviations of analog sensor.Load sensitivity is clear Depend on to Chu the property of substrate.For stretching, the power of applying is significantly larger, and load sensitivity is smaller.

Therefore, in both bending facility (Fig. 9 A-9B) and stretching facility (Figure 11 A-11B), property and survey in substrate All there is directly contact between the load sensitivity of amount.It is non-linear to be attributed between ETP-MCNP films and various substrates not Same adhesiveness.It may be evident, however, that the property by controlling substrate, using identical MCNP parts, can adjust load sensitivity. This is eliminated to for producing different MCNP with the need of a large amount of and expensive building-up process of the sensing function needed for reaching Will.

Embodiment 4：To fine-tuning for the sensing property of flexible MCNP sensors

In order to determine the factor of the load sensitivity for controlling sensor, following additional parameter is checked：(i) electrode gap； (ii) substrate relevant parameter (such as width)；(iii) MCNP films relevant parameter (for example coating part).In order to determine electrode Interval effect, casts ETP-MCNP layers in the electrode gap of 0.5-3mm scopes.For specific electrode gap, error line is 3 The standard deviation of the sensor of individual test.It is negligible that Figure 12 A show that the interval between electrode has to load sensitivity Effect.Conversely, the interval between electrode greatly changes baseline electrical resistance.For example, the ETP- cast in the electrode gap of 1mm MCNP films show the exemplar baseline resistance of 4 Μ Ω, and the similar ETP-MCNP films cast in 3mm electrode gaps show 8 Μ Ω Baseline electrical resistance (Figure 12 A).Do not constrained by any theoretical or mechanism of action, it is considered to which load sensitivity does not rely on baseline electricity Resistance.The image of electrode structure is given in the illustration of Figure 12 A.

Figure 12 B are demonstrated using with different base sizeETP-MCNP layers cast on 127 can To control load sensitivity.Error line in figure is located at 3 weights of the identical sensor in the substrate with specific dimensions Multiple standard deviation.10mm is cut into from 30mm by by base widths, load sensitivity improves 3.5 times.

By changing the additive factor that MCNP layers of cladding provides the sensitivity of flexible sensor of the control based on MCNP. The organic ligand of MCNP determines the type and intensity of the chemical bond between adjacent MCNP, so as to influence load sensitivity.Determine The tunnel attenuation constant of resistance variations is also influenceed by cladding part.Figure 12 C give to work as and cladding part are replaced with into nitre from ETP Two kinds of MCNPS are simultaneously cast in 5 kinds of different substrates (by them in x- axles by base -4- TRIFLUORO-METHYLs benzenethiol (NTMBT) Young's modulus E and their rotary inertia I represent) on when load sensitivity change.Error line is 3 analog sensors Standard deviation.For both ETP-MCNP and NTMBT-MCNP films, there is positive correlation between load sensitivity and base property.To the greatest extent Pipe is in this way, all NTMBT-MCNP sensors show relatively low load sensitivity.

Therefore, by adjust base widths and/or change MCNP sensors in cladding part, can obtain to load spirit The control of sensitivity.

Embodiment 5：Flexible MCNP sensors are used as strain gauge

Figure 13 shows the calibration factor (GF) of ETP-MCNP sensors (asterisk).GF is measured the sensitivity table of sensor It is strain gauged to levy, i.e. Δ R/R_bRatio and ε between.GF is as the relative response curve of the sensor of function of strain The slope of linear fit.In facility is bent, strain is proportional to substrate thickness, and GF is inversely proportional with the thickness of substrate.Figure 13 shows Show that the antilinear between GF and substrate thickness is related.250 GF can utilize the ETP- deposited in thin substrate (36 μm) MCNP films are realized.Answering based on nano particle of this GF value than the former report given by open circles in fig. 13 and table 2 Become metering at least twice high.

The gage probe of table 2.

^(a)PET=PETs

^(b)LDPE=low density polyethylene (LDPE)s

^(c)Farcau et al., ACS Nano2011,5,7137-7143

^(d)Tsung-Ching et al., J.Disp.Tech.2009,5,206-215

^(e)Vossmeyer et al., Adv.Funct.Mater.2008,18,1611-1616

^(f)Herrmann et al., Appl.Phys.Lett.2007,91,183105

What is proved herein is to use sensor of the invention and matrix as super-sensitive strain gauge.Commercially available strain gauge The typical calibration factor be 2.MCNP strain gauges have adjustable calibration factor, and the calibration factor is influenceed simultaneously by substrate thickness And can be controlled by substrate thickness.

Embodiment 6：The fatigue behaviour of flexible MCNP sensors

Using in flexibilityTested big as the three kinds of sensors of sensed layer with ETP-MCNP in 127 substrates Fatigue behaviour in amount flexure cycles.Sensor is set to undergo for 0.3% 10,000 cycles of strain.In a sensor, base Line resistance significantly changes, and thus be excluded that the sensor.Other two sensors (S1 and S2) are displayed in increase flexure cycles Number of times after baseline electrical resistance drift (Figure 14 A-14B).The maximum drift of baseline electrical resistance is~9%.Not by any theoretical or work With the constraint of mechanism, although part drift may be attributed to sensor in itself, at least some drifts may be attributed to the measurement phase Between temperature and relative humidity change.With baseline electrical resistance conversely, 10, after 000 flexure cycles, Δ R/R_bIt is only slight to change (2%).Therefore, display ETP-MCNP sensors show excellent fatigue behaviour.

Embodiment 7：Sensed using the temperature and humidity of flexible MCNP sensors

Checked on the ETP-MCNP sensors installed on the pet substrate and use the touch platform intergration temperature based on MCNP With the possibility of relative humidity (RH) sensing function.In order to test the response of sensor for temperature and RH, sensor is placed in tool In having a vacuum chamber of controllable environment.Temperature and RH are independently variable, and monitor corresponding Δ R/R_b.Figure 15 A are given 20% Constant RH levels under rise high-temperature after sensor Δ R/R_b(Figure 15 A, illustration).ΔR/R_bReduce with humidity index (Wuelfing et al., J.Phys.Chem.B2002,106,3139-3145).For practical purpose, in 23-39 DEG C of temperature model Interior often 1.66 DEG C of temperature of increase are enclosed, normalized resistance reduces~1%.Figure 15 B are shown present in most of environmental applications The Δ R/R of the sensor based on ETP-MCNP in humidity regions (5-60%RH)_b.Sensing is tested under 25.5 DEG C of steady temperature Device (Figure 15 B, illustration).There is approximately linear increase in the sensing signal of the function as RH levels, sensitivity drops to list Individual RH percentages.

Accordingly, it is considered to the sensitivity for being based on the sensor of ETP-MCNP is high enough that uses the linear of sensor relative response The approximate resolution ratio detection temperature with less than 1 DEG C fluctuates, and detects moisture fluctuation with the resolution ratio of~1%RH.Biography of the invention Therefore sensor and platform can serve as the thermal source of such as human body temperature meter or sensing manually or near electronic skin, without touching Touch object.

Embodiment 8：Touch-sensing application

Proof of the MCNP sensors as the ability of touch sensor is carried out by using Morse code coding letter.Rub Your this code is the combination of long and short pulse (line and point), its coding whole alphabet and 10 numerals (Figure 16 A).By by hand Refer to by short and long period is continued on a sensor, obtain on each sensor to the detection of these signals.Electric signal changes Into the information on pressure amplitude and pressure duration.Based on this operation mode, two kinds of different signals (short resistance are obtained Response is defined as a little, and electrical response long is defined as line) (pressure rough estimate is single KPa).Using in 125 μ m-thicks The sensor of the ETP-MCNP deposited in PET base.The sensed layer of ETP-MCNP is downwards during pressing so that in finger and Directly contact is not formed between ETP-MCNP layers.In this way, humidity of skin and temperature are minimized to the influence for sensing.Heavy Product is pressed on the ETP-MCNP films in 125 μ m-thick PET bases and produces firm, accurate and repeatable signal (Figure 16 B). Similar result is obtained using the pressure sensor based on DT-MCNP.It is being deposited on different substrates, i.e. 36 μ m-thicks On similar ERP-MCNP films on generation × 20-30 times higher of response (Figure 16 C) of pressing.Accordingly, it is considered to the thickness pole of substrate The response of earth effect sensor.

Accordingly, it is considered to load sensitivity can be adjusted by using different substrates.Therefore, it can design to different load The sensitive sensor matrices of scope (being for example adapted for children and adult).Other application includes wherein requiring that sensing is less than The endovascular neurosurgery of the load of 200mg is performed the operation, changed with the load more than 1,000Kg with small load sensitivity (transduce) seat belt sensor, or wherein require the surgery of scoliosis of high load capacity strain gauge.

Now most of touch panels be based on ON/OFF sensing mechanism, wherein equipment can sense applying load but can not Determine the load (Walker, J.Soc.Info.Disp.2012,20,413-440).Platform unit of the invention not only has sense Survey the ability that the ability for touching also has sensing payload.Adjustment is allowed to the spy required for application-specific using various substrates The sensing property of constant load scope.

Embodiment 9：For composite measurement pressure, the sensing platform based on MCNP of temperature and humidity

Demonstrate herein and various parameters are sensed from complex sample (for example, pressure, temperature using single flexible sensing platform Degree, humidity).Prepare the prototype based on MCNP technologies and assess the load of its measurement environment temperature, relative humidity and applying Ability.Using different substrates to eliminate the load sense of the part from sensor, and select different cladding parts To isolate the sensing to relative humidity or temperature.By the ETP- that cast on the silica of the interdigital gold electrode with evaporation MCNP and NTMBT-MCNP manufactures two kinds of sensors.By the ETP-MCNP that cast in the PET base with 1mm electrode gaps To manufacture 3rd sensor, as shown in Figure 17.

Temperature and humidity is calculated using non-flexible sensor.In order to sense relative humidity, such as Segev-Bar et al., J.Phys.Chem.C.2012,116,15361-15368 --- entire contents are incorporated to whereby --- are described, using there is hole NTMBT-MCNP films.Due to ionization mechanism, the sensor has big Negative Acknowledgment (up to 80%) for increased RH levels. Such as visible in Figure 18 A-18B, relative responses of the NTMBT-MCNP to 55%RH is for about -70%, and to test scope (23- 38 DEG C) in temperature maximum relative response be 15%.In order to sense major temperature change, the ETP-MCNP solution of high enrichment (50mg/ml) casts on silicon oxide substrates, obtains the film (being estimated by AFM) of 500nm thickness.The thickness of film is than evaporation The thickness (350nm) of gold electrode is big, the latter can cause possible expansion (Steinecker et al., Anal.Chem.2007,79, 4977-4986).As seen in Figure 18 C-18D, for whole RH range (22-63%RH), in silica substrate The ETP-MCNP layers of response to relative humidity in noise range (± 1%), and when increase temperature when relative response decline it is (right In every 1 DEG C change, Δ R/R_b~1.35%).

Prototyping Platform is exposed to different temperature and the relative humidity cycle of room conditioning control.RH range For 33-60% and temperature range are 15-22 DEG C.Relative humidity is modeled by the linear fit in Figure 18 A, and temperature passes through Figure 18 D In Arrhenius fitting modeling.The mean error for carrying out 6 values of different cycles of free external sensor measurement is summarised in table In 3.When the cycle is averaged out, temperature-averaging error is 4.8% ± 1.4%, and RH mean errors are 9.3% ± 7%.

The summary of 3. pairs of degrees of accuracy using S1 and S2 measurement temperatures and RH of table

In order to assess performance of the Prototyping Platform in terms of load is sensed, apply unknown negative on flexible ETP-MCNP sensors Lotus.It is desirable for this purpose that explaining the algorithm of temperature, RH and load.Generally, the resistance variations for giving sensor are three parameters The factor：Temperature, RH and load.The effect of each parameter can be linear or nonlinear.However, as disclosed herein, Can model and measure the sensor resistance for causing due to RH and temperature change under-the specified load.In order to prove easily to model RH With the ability of the effect of temperature, several experiments are carried out.Sensor is exposed to certain by under the conditions of 2 different constant RH Temperature range (23-38 DEG C) (Figure 19 A) and under 3 stationary temperatures by sensor be exposed to certain RH scopes (22- 63%) (Figure 19 B) sets up temperature and RH on the correlation between sensor resistance.Figure 19 A show that sensor response is right The Arrhenius dependences of various temperature.The line of 2 different RH conditions is parallel.For small temperature range (~5 DEG C), the temperature dependency of sensor can be approximated to be linear.Figure 19 B also show that increase RH levels after dominant linear and Parallel response (in addition to the step in the 20%RH at 30 DEG C).Due to RH can not possibly be maintained when temperature is changed>25% Controlled condition, it is contemplated that the behavior represent whole test scope (Konvalina et al., ACS Appl.Mater.Interf.2012,4,317-325).The response of ETP-MCNP sensors is to temperature (T) and relative humidity (RH) Dependence can be described approx with following equation：

R=R_Baseline+ΔR_RH·RH+ΔR_T·T

Wherein R is the measurement resistance of sensor；ΔR_RHIt is the resistance variations of per unit relative humidity variations；ΔR_TIt is every list The resistance variations of position temperature change；And R_BaselineIt is the reckoning resistance at 0 temperature and RH.Linear model is used for the sake of simplicity. Based on this equation, the response of flexible ETP-MCNP sensors can be described as the plane in resistance v. temperature-RH spaces.

As described above, under the conditions of changing environment, measurement is based on three prototypes of sensor.Checked under different loads Flexible ETP-MCNP sensors.Flexible ETP-MCNP sensor for temperature (Δ R_T) and relative humidity (Δ R_RH) response for not It is different with load, and is calculated using the solver scripts in Microsoft.The |input paramete for using is：It is different Environmental condition (temperature and relative humidity) and flexibility ETP-MCNP sensors corresponding resistor.

Figure 20 describes the temperature and phase of the load (load 2) in 0 load (load 0), the load (load 1) of 3gr and 6gr To the different dependences of flexibility ETP-MCNP sensors under humidity.Temperature and relative humidity by non-flexible ETP-MCNP and NTMBT-MCNP sensors (Figure 18 A-18D and 19A-19B) are calculated.As seen in Figure 20, when different loads are applied, to temperature The relative response of degree and relative humidity changes (for example, Δ R_RHWith Δ R_TDepend on load).

Table 4. deposits calculating and applying the load on ETP-MCNP sensors on the pet substrate

By measuring load sensitivity of the ETP-MCNP sensors in PET base at specific temperature and RH, it is based on The plan be given in Figure 20 calculates the relative response of sensor under these conditions, and calculates what is applied based on the data Power carrys out the accuracy of evaluation model.Result is summarised in table 4.Result clearly demonstrate that the ability of model evaluation load, variance Less than 20%.

Set forth herein matrix prototype using the different MCNP in non-flexible substrates, so as to being not associated with (un- Conjugated mode sensing temperature and humidity (being the single-sensor for sensing only temperature or relative humidity)).Calculated after measurement Method is used for flexibility ETP-MCNP sensors, so that load sense is isolated with other specification (temperature and humidity).When applying load When, the expansion distance between nano particle changes surface coverage, and this causes morphological change.These change influence MCNP and pass Sensor is responded.In the case of the effect of temperature and RH to resistance is nonlinear, correlation can be modeled, and draw representational non- Linear plane, its parameter needed for making it possible to measurement.

Embodiment 10：Via the integrated load of layer by layer deposition, temperature and RH sensors (3 close 1)

With lauryl amine coat gold nano grain (DA-GNP) via successively (LBL) technology deposit (Joseph et al., J.Phys.Chem.C.2007,111,12855-12859；With Vossmeyer et al., Adv.Funct.Mater.2008,18, 1611-1616) existIn substrate, the substrate have with different shape and interval two electrode pairs (S1 and S2).S1 has 10 pairs of interdigital structures of Au electrodes (100 μm of 100 μm of intervals between width and adjacent electrode).S2 and S3 have 2 electrodes, between them at intervals of 100 μm.The different baseline electrical resistance for S1 and S2 is produced using different electrode pairs (being~150 Κ Ω for S1, be~4100 Κ Ω for S2).Therefore, passed by using different electrode structure manufacturing environments Sensor, obtains the difference response to temperature and humidity.S3 is placed downwards towards estrade, it is ensured that part and ambient shield.In base Small window is carved in bottom allows physics when towards estrade compression sensor to sink (Figure 21 A).The resistance of sensor is in room Between measure under environmental condition.The temperature and relative humidity in room are by independent (outside) sensor record.It is carried out as follows and separates Three features (pressure, relative humidity and temperature)：Both S1 and S2 are measured under different conditions.Test temperature scope is 21.5 DEG C -26 DEG C, and RH range is 55-85%.Algorithm calculates and is used for calculating RH and T parameters after measurement, and by the 3rd ring The sensor settings of border protection are for while sensing touch.Due to different electrode structures, each sensor i is to temperature (Δ R_iT) and Relative humidity (Δ R_iRH) dependence be different, and be based on 13 surveys using the solver scripts in Microsoft Excel Amount group (set) is calculated.As input, in following equation using different environmental condition (temperature and relative humidity) and The corresponding resistor of each in two sensors：

R_i=R_{I baselines}+ΔR_iRH·RH+ΔR_iT·T

Wherein R_iIt is the measurement resistance in a certain RH and temperature (T) condition lower sensor i, and R_{I baselines}It is in 0 temperature and RH Under reckoning resistance.Based on two sensors that Different Plane is formed in resistance v. temperature-RH spaces, within the mode meter penetrated Calculate temperature and relative humidity (Figure 21 B).

5. pairs of summaries of the model accuracy sensed using S1 and S2 temperature and RH of table

In order to test the accuracy of the model of reception, by external sensor measurement resistance under difficult environmental conditions Three additional points, and calculated by the equation being fitted.Result is given in Table 5.Intermediate sensor (S3) downwards is to humidity It is less sensitive with temperature change, and the effect to resistance in whole process of the test is less than 1%.Compare, as applying about 15KPa Pressure when, because the response that the bending of substrate causes is for about 2% (Figure 21 C).Therefore, S3 can be used with the test limit of 15KPa Sensing pressure, because temperature and relative humidity are to sensor when compared with by applying the signal magnitude that pressure is obtained Effect is inapparent.Therefore, for the pressure higher than 15KPa, change environmental condition caused by noise be it is negligible, And can easily measure pressure.The model can evaluate environment temperature and relative humidity (table 5).Therefore, by combining tool There are three sensors and coordination electrode shape and the direction of similar nanoparticle coating, measurable all three parameter.

Therefore, by using 3 arrays of sensor --- wherein load sensor be protected against ambient influnence and Other two sensors are protected against mechanical bias, can obtain multi-parameter sensing.These results prove production and by temperature The possibility of artificial or electronic skin application the part based on MCNP is integrated into humidity sensor.Therefore, can be used single (or similar) MCNP is chemical to realize the such as temperature, relative of the multi-parameter in identical platform with various underlying structure/designs Humidity and load sense.

It should be understood by those skilled in the art that the present invention is not limited by being above particularly shown with description content.And It is that the scope of the present invention includes combination and the sub-portfolio of each feature mentioned above, and changes and modifications.Therefore, this hair The bright implementation method that should not be construed as limited to specifically describe, and this will be better understood by referring to appended claims The scope and spirit of invention.

Claims (27)

1. a kind of platform unit for detecting the parameter selected from pressure, temperature, humidity and combinations thereof, the platform unit bag Include：Multiple sensors, the sensor includes the metal nanoparticle coated with organic coating, wherein the multiple sensor bag Include：

I. at least one pressure sensor in the substrate of flexibility is deposited on, wherein the pressure sensor is configured to sensing applying It is added in pressure thereon and in response to the pressing creation electric signal；With

Ii. at least one humidity sensor, it is configured in response to humidity change and shows the organic coating cladding The metamorphosis of metal nanoparticle, and electric signal is generated in response to the metamorphosis, wherein at least one humidity Sensor includes dual sensing sensitivity, and thus the multiple sensor provides the inspection to pressure, temperature, humidity or their combinations Survey.

2. platform unit according to claim 1, further includes at least one temperature sensor, and it is configured to Temperature change shows the metamorphosis of the metal nanoparticle of the organic coating cladding, and becomes in response to the form Metaplasia is into electric signal.

3. platform unit according to claim 1, further includes the multiple electrodes comprising conductive material, wherein described many Individual electrode is coupled and for measuring the signal generated by the sensor with each sensor.

4. platform unit according to claim 1, wherein each sensor are sensed with selected from capacitance sensor, resistance-type The form configuration of device, resistive chemisensor, impedance transducer and field effect transistor sensing device.

5. platform unit according to claim 1, further includes detection means, it include for measure resistance, conductance, The device of the change of alternating current (AC), frequency, electric capacity, impedance, inductance, mobility, potential, optical property or voltage threshold.

6. platform unit according to claim 1, further includes film, wherein the film is configured to blocking at least one Sensor is in response to humidity change generation signal.

7. platform unit according to claim 6, wherein the film is characterised by that the scope of thickness is 1 μm -1000 μm.

8. platform unit according to claim 6, wherein the film is selected from epoxy resin, silicones, polyamide, poly- Imide resin, poly- p- xylylene resin and combinations thereof.

9. platform unit according to claim 1, wherein the pressure sensor is configured to generation and described flexible The electric signal of the offsets in proportion of substrate.

10. platform unit according to claim 1, wherein the feature of the flexible substrate is width in 0.01-10cm In the range of and thickness in the range of 20-500 μm.

11. platform units according to claim 1, wherein the flexible substrate includes polymer.

12. platform units according to claim 11, wherein the polymer be selected from polyimides, polyamide, polyimides, Polyethylene, polyester, dimethyl silicone polymer, polyvinyl chloride and polystyrene.

13. platform units according to claim 2, wherein the temperature or humidity sensor are deposited on flexibility or rigidity In substrate.

14. platform units according to claim 13, wherein the rigid substrate be selected from metal, insulator, semiconductor, Semimetal and combinations thereof.

15. platform units according to claim 1, wherein the metal nanoparticle be selected from Au, Ag, Ni, Co, Pt, Pd, Cu, Al and combinations thereof.

16. platform units according to claim 1, wherein the metal nanoparticle is selected from Au/Ag, Au/Cu, Au/ The metal alloy of Ag/Cu, Au/Pt, Au/Pd, Au/Ag/Cu/Pd, Pt/Rh, Ni/Co and Pt/Ni/Fe.

17. platform units according to claim 1, wherein the organic coating comprising selected from alkyl hydrosulfide, aryl mercaptan, Alkylaryl thiol, alkyl sulfide alkoxide, omega-functionalized alkanethiol salt, arene thiolate, γ-mercaptopropyi trimethoxy silicon The compound of alkane, dialkyl disulphides and combinations thereof and its derivative.

18. platform units according to claim 1, it include being deposited on dual-temperature in the substrate of flexibility or rigidity and Humidity sensor.

19. platform units according to claim 1, it includes that the dual-pressure being deposited in the substrate of flexibility and humidity are passed Sensor.

20. platform units according to claim 1, it includes that the dual-pressure being deposited in the substrate of flexibility and temperature are passed Sensor.

21. platform units according to claim 2, it includes two sensors, and one of sensor is deposited on soft Property substrate on dual-pressure and humidity sensor, and another sensor be deposited on flexibility substrate on dual-pressure And temperature sensor.

22. platform units according to claim 1, wherein use measuring calculating or its combination extraction after preceding calibration, measurement The signal generated by each parameter.

23. platform units according to claim 1, wherein the humidity sensor includes the metal coated with organic coating The both continuously and discontinuously region of nano particle.

24. platform units according to claim 23, wherein the discontinuity zone includes that size range is 10nm- The space of 500nm.

25. platform units according to claim 24, wherein the discontinuity zone includes the sky between 3% and 90% Gap.

26. platform units according to claim 1, it also includes analyte sensor, wherein the analyte sensor Sensing is configured to adsorb analyte thereon and generate electric signal in response to the analyte.

27. platform units according to claim 1, it is integrated on electronics or artificial skin surface.